Diffusion and sorption studies of dyes through PVA cryogel membranes

The capacity of poly(vinyl alcohol) (PVA) to crosslink through freeze/thaw method was used to obtain PVA hydrogel membranes (HG) that were subjected to sorption and diffusion experiments using three dyes: Congo red (CR), methylthymol blue (MTB), and crystal violet (CV). To study the sorption of dyes into the cryogenic membrane, dye solutions at different concentrations were used. After sorption, desorption of dyes from the PVA membrane was monitored to quantify the possible regeneration of the membrane (PVA HG). To have a deep insight on the mechanism behind the desorption process, dye‐release kinetics were studied. The diffusion experiments reveal the fact that CR and MTB do not permeate the PVA HG membrane making it a promising candidate in the advanced purification processes of wastewaters. The effect of the incorporation of dyes (CV, CR, and MTB) on the chemical properties of PVA cryogel matrices has been studied by using several techniques such as: differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and Fourier transform infrared (FTIR) spectroscopy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Calixarene-based extractants for heavy metal ions removal from aqueous solutions

The article reviews the literature on the possibility of application of the calixarene-based compounds for selective separation of toxic heavy metals from aqueous solutions by the solvent extraction and transport across liquid membranes. The specific three-dimensional structure of calixarenes and their derivatives, simple and low-cost synthesis, and ease of chemical transformation qualify these compounds for the role of selective chemical extractants of toxic heavy metal ions present in industrial wastewater. This article analyses the influence of various process factors, with the greatest emphasis on the structure of the extractants/carriers, on efficient separation of heavy metal ions, primarily those most commonly found in galvanic wastewater.     

Adsorption of some heavy metal ions from aqueous solutions on Nafion 117 membrane

Nafion 117 membrane was investigated for the removal of Ni(II), Co(II), Pb(II), Cu(II) and Ag(I) metal ions from their synthesized aqueous solutions. The different variables affecting the adsorption capacity of the membrane such as contact time, initial metal ion concentration in the feed solution, pH of the sorption medium and temperature of the solution were investigated on a batch sorption basis. The affinity of Nafion 117 membrane towards heavy metal ions was found to increase in the sequence of Cu(II), Ni(II), Co(II), Pb(II), and Ag(I) with adsorption equilibrium achieved after 30 min for all metal ions. Among all parameters, pH has the most significant effect on the adsorption capacity, particularly in the range of 3.1-5.9. The variation of temperature in the range of 25-65 °C was found to have no significant effect on the adsorption capacity. Nafion 117 membrane was found to have high stability combined with repeated regeneration ability and can be suggested for effective removal of heavy metal ions such as Cu(II), Ni(II) and Co(II) from aqueous solutions.     

New sorbent hydrogels for removal of acidic dyes and metal ions from aqueous solutions

Summary Poly(N-hydroxymethylacrylamide), PHMA, hydrogels were prepared by using N-hydroxymethylacrylamide, HMA, monomer and polyethyleneglycol(400)diacrylate as a crosslinking agent in aqueous medium and then amine groups were incorporated onto PHMA hydrogels by amination reaction with different diamines. The obtained hydrogels were characterized by determination of amine value, hydroxymethyl group content and FTIR spectra. The amine value of hydrogels changed from 2.23 to 4.64 mmol/g by depending on the amine compounds used in amination reaction. Their swelling degree increased at acidic pH values and they showed pH dependent swelling behaviour. They were used as sorbent for removal of indigo carmine and Cu(II) ion, as a model dye molecule and metal ion, respectively, from aqueous solutions. The adsorption properties of the hydrogels were investigated by depending on pH, time and initial indigo carmine or Cu(II) ion concentration. It was seen that the amine group incorporated hydrogels have quite high adsorption rate and adsorption capacity, and their adsorption capacities changed with pH of the solution. Langmuir isotherm model was the best fit for adsorption of both indigo carmine and Cu (II) ion.     

Polyelectrolyte CASA hydrogels for uptake of uranyl ions from aqueous solutions

In this study, uranyl ion adsorption from aqueous solutions has been investigated by chemically crosslinked acrylamide/sodium acrylate (CASA) hydrogels. Adsorption studies were investigated by the spectroscopic method. CASA hydrogels with various compositions were prepared from ternary mixtures of acrylamide (A), sodium acrylate (SA), and water by free radical polymerization in aqueous solution, using multifunctional crosslinkers such as ethylene glycol dimethacrylate (EGDMA). Uranyl ion adsorption from aqueous solutions was studied by the batch sorption technique at 25°C. The effect of uranyl ion concentration and mass of adsorbent on the uranyl ion adsorption were examined. In experiments of sorption, L‐type sorption in the Giles classification system was found. Some binding parameters, such as initial binding constant (K_i), equilibrium constant (K), monolayer coverage (n), site‐size (u), and maximum fractional occupancy (Ô) for the CASA hydrogel–uranyl ion binding system, were calculated using the Langmuir linearization method. Finally, the amount of sorbed uranyl ion per gram of dry hydrogel (q) was calculated to be 4.44 × 10^?4–14.86 × 10^?4 mol uranyl ion per gram for CASA hydrogels. Adsorption of uranyl ion (percentage) was changed within a range of 12.86–46.71%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 200–204, 2007     

Removal of metal ions in fixed bed from multicomponent solutions using N-(2-sulfoethyl) chitosan-based sorbents

This work focuses on the dynamic removal of transition and alkaline earth metal ions using N-(2-sulfoethyl) chitosan-based sorbents (NSE) with various degrees of substitution (DS) in fixed-bed columns. The breakthrough curves for Ag(I), Cu(II), Co(II), Ni(II), Zn(II), Mn(II), Cd(II), Mg(II), Ca(II), Sr(II), Ba(II) and Pb(II) ions sorption onto chitosan-based materials were obtained. Experimental data allows concluding that the mechanisms of sorption of these metals are different. Thomas, Adams-Bohart and Yoon-Nelson models were applied to the experimental data to predict the breakthrough curves and the rate constants. The surface of chitosan-based materials could be fully regenerated by a 0.1 mol/dm³ nitric acid solution.     

Adsorption of heavy metal ions from aqueous solutions by porous polyacrylonitrile beads

The adsorption of Cu(II), Ni(II), Zn(II), and Pb(II) from aqueous solutions on acrylonitrile copolymer sorbents was studied. We prepared five types of sorbents from polyacrylonitrile by varying its concentration in the initial polymer solution and the composition of the coagulation bath, aiming to achieve a different porous structure. The specific area, pore volume, and pore radius of the sorbents were determined on a porosimeter. The porous structure was studied by scanning electron microscopy. Modification of sorbents with sodium hydroxide and hydroxylamine was carried out to form amidooxyme and carboxylic groups with proven complex‐forming properties toward heavy metal ions. The optimal pH of the sorption of metal ions was found. The adsorption kinetics were investigated. The order of polymer sorbents toward the sorption of Pb(II), Cu(II), Ni(II), and Zn(II) ions, and the order of heavy metal uptake were determined for all types of sorbents. The effectiveness of heavy metal desorption and the coefficient of recovery of sorption ability were determined. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3036–3044, 2002; DOI 10.1002/app.2334     

双水相体系萃取分离金属离子研究进展

双水相体系是一种绿色环保的新型分离技术,应用领域相当广泛,是近年来的研究热点。论述了双水相体系用于萃取分离金属离子的研究现状。根据所使用萃取剂的不同分3种情况进行了论述：不添加任何萃取剂直接萃取金属离子;以无机阴离子为萃取剂,依靠金属阳离子与无机阴离子形成的阴离子配合物（螯合物）而转移到萃取相,萃取金属离子;采用有机试剂作为萃取剂,依靠金属离子与萃取剂反应形成的中性配合物（螯合物）而转移到萃取相,萃取金属离子。论述了双水相体系萃取分离金属离子的发展趋势：建立金属离子在双水相体系中分配的机理模型;双水相体系成相物质的回收及再利用;通过无机盐水化能力的差异,或者通过双水相体系的温度诱导相分离,实现无机盐的分离与常温制备;开展双水相体系萃取分离金属离子的工程研究。     

Sorption of heavy metal ions from aqueous solutions in the presence of EDTA on monodisperse anion exchangers

Conventional precipitation methods of industrial sewage and wastewater purification are not very effective and are insufficient in many cases. This implies the necessity of searching new, effective methods exploiting cheap, accessible and ecologically safe ion exchangers and sorbents. The paper presents the studies on removal of heavy metal ions — Cu(II), Zn(II), Co(II), Ni(II) and Fe(III) — from aqueous solutions in the presence of EDTA carried out on commercially available, strongly basic monodisperse anion exchangers with the polystyrene skeleton gel, Lewatit MonoPlus M 500; and the macroporous, Lewatit MonoPlus MP 500, which are more widely applied in water purification processes. The research results indicate a high affinity of the Lewatit MonoPlus M 500 and Lewatit MonoPlus MP 500 anion exchangers in the chloride form for copper(II), nickel(II), cobalt(II) and zinc(II) complexes with EDTA. The affinity series for the heavy metal complexes in the 0.001 M M(II)/(III)–0.001 M EDTA and 0.001 M M(II)/(III)–0.001M EDTA–0.001 M–0.002 M NaOH systems were found for the Lewatit MonoPlus M 500 anion exchanger in the chloride form to be as follows: Cu(II) > Ni(II) > Co(II) > Zn(II) Fe(III). In the case of the Lewatit MonoPlus MP 500 anion exchanger in the chloride form there was found the following affinity series: Cu(II) > Co(II) > Ni(II) > Zn(II) Fe(III). These anion exchangers can be applied in the removal of copper(II) complexes from waters and wastewaters.     

Polyamine functionalized glycidyl methacrylate terpolymers as scavengers for metal ions uptake from organic solutions

Resins with amine functionalities were obtained as a result of chemical modification of low crosslinked terpolymers of glycidyl methacrylate with styrene and divinylbenzene or diethylene glycol dimethacrylate. The loading of amine groups, swelling in the selected organic solvents, and thermal properties of the resins were studied. FTIR, DSC, TGA, SEM, and stereomicroscopy methods were also applied for exploring of the resins. The amine functionalized resins were tested as sorbents for uptake of cobalt(II), copper(II), iron(III), and manganese(II) ions from methanol and its mixtures with methylene chloride. The study show that all polyamine functionalized resins uptake quickly Cu(II) ions from methanol solutions. Their ability to remove cobalt(II), iron(III), and manganese(II) ions from solution depended on the mutual compatibility of solvents and resins. It increases clearly when the mixtures of methanol and methylene chloride are applied. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Recent review for removal of metal ions by hydrogels

A continuous research is going to synthesize the novel adsorbents for removal of toxic metal ions having high sorption capacity along with non-toxic and biodegradable nature. Ionic impurities have been removed in many ways. However, hydrogels with high sorption capacity, high functionality, hydrophilicity, regeneration and nontoxicity have made them a good contender for the removal of various aquatic pollutants, including heavy metal ions. Moreover, certain modifications in synthesis of hydrogels, to customize them in response to different stimuli like temperature, pH and ionic strength, has added an advantage in waste water treatment. The present review provides recent progress in the synthesis of the hydrogels for waste water treatment and insight into increase in selectivity, efficiency and reusability of hydrogels.     

Simultaneous removal of humic acid and heavy metal from aqueous solutions using charged ultrafiltration membranes

Lab-made negatively charged ultrafiltration (UF) membranes were used for simultaneous removal of humic acid (HA) and heavy metals from water. Effects of the HA/metal ratio, solution pH and ionic strength on rejection coefficients of HA and metals were investigated. The results showed that the rejection coefficients of both HA and metals increase with the increase of pH and the HA/metal ratio, and the decrease of ionic strength. This study indicated that charged UF could be an effective method for the simultaneous removal of HA and heavy metal harnessing the principle of complexation UF and electrostatic repulsion between the membrane and the HA–M complex of the same charges.     

Application of a carbon sorbent for the removal of cadmium and other heavy metal ions from aqueous solution

Treatment of flax shive with sulfuric acid produces a carbonaceous material that has been used to remove metal ions from aqueous solution. Metal ions including Cd(II), Cu(II), Cr(III), Co(II), Ni(II), Zn(II) and Pb(II) have been investigated for kinetic behaviour and sorption capacities. These metal ions show fast sorption kinetics following a first order rate equation. Cadmium was chosen as representative of these metal ions and a detailed study was carried out. The effect of pH on sorption was studied and it was found that maximum uptake occurred above pH 3–7, sorption was accompanied by release of protons into the solution and a ratio of [H⁺] released to [Cd²⁺] sorbed of approximately 2 was found. The sorption capacity showed no significant increase with increase of temperature. The presence of other metal ions such as K⁺, Na⁺, Mg²⁺ and Ca²⁺ decreases the Cd(II) capacity, indicating competition for the ion exchange sites. Successive sorption of Cd(II) shows that the capacity exceeds the monolayer capacity calculated from the Langmuir equation. Column studies showed good performance over a total of seven cycles of loading/stripping. These studies indicate that the sorption mechanism for these metal ions is related to a reversible ion exchange process on the carbon surface. © 2002 Society of Chemical Industry     

Study of polymer‐metal ions triple complex as materials for adsorption and separation

Diethylenetriamine and a copolymer of sodium acrylate and maleic anhydride were used for the adsorption and separation of Au³⁺, Ru³⁺, Bi³⁺, and Hg²⁺ ions by forming polymer‐metal ions triple complex. The acidity, temperature, capacity, and interference on the adsorption of these ions on the complex, as well as the conditions of desorption of these ions from the complex, were investigated by means of inductively coupled plasma optical emission spectrometry. The results were satisfactory. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 819–821, 1999     

Polyethyleneimine‐grafted membranes for simultaneously adsorbing heavy metal ions and rejecting suspended particles in wastewater

Heavy metal ions (HMIs) in wastewater can be removed by polyethyleneimine (PEI) adsorption, however, it is difficult to recycle PEI macromolecules from their mixture with suspended particles in wastewater. A novel HMIs adsorption technique with renewable PEI‐grafted porous membranes was developed. PEI molecules were dispersed with high specific area and structured morphology, which allowed HMIs and suspended particles to be retained separately at different locations of the membrane, with the former adsorbed in matrix and the latter rejected on surface. The membranes with the optimized PEI loading ratio of 30 k wt % behaved excellently with microsphere rejection and Co(II) adsorption reaching 98.5% and 51.0 mg/g, respectively. They successfully decreased Co(II) concentration from 3.0 mg/L to the allowable discharge standard (0.5 mg/L), even with an enhanced flux of 6200 L/m²/h at 0.12 MPa under the cyclic tests. Overall, PEI‐grafted membrane adsorption is highly efficient for removing HMIs and suspended particles simultaneously from wastewater. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4541–4548, 2017     

水凝胶材料在金属离子富集与分离领域的研究进展

水凝胶作为一种极具前景的吸附剂材料,由于具有高效、易操作且能耗低的特性,被广泛应用于工业废水和环境污水中金属离子的富集与分离。近年来,随着主-客体识别作用与金属离子配位作用研究的不断深入,利用水凝胶材料选择性分离和富集金属离子成为研究热点。本文综述了水凝胶材料在富集和分离特定金属离子领域的研究新进展,重点介绍了利用水凝胶材料特异性分离和富集放射性金属离子、稀土金属离子、贵重金属离子和重金属离子的研究现状。     

Synthesis of a carbamide-based dithiocarbamate chelator for the removal of heavy metal ions from aqueous solutions

This study was carried out to develop a carbamide-based dithiocarbamate (CDTC) chelator for the removal of heavy metal ions from wastewater. Its structural properties were characterized by FT-IR, ¹H NMR and ¹³C NMR. Results confirmed the functional groups of HNC(S)S existed. The adsorption isotherms showed CDTC had a high adsorption capability for Zn (119.8 mg/g) and Cu (63.1 mg/g). It exhibited a distinctive selectivity for the removal of metal ions (Cu²⁺ > Zn²⁺ > Cr³⁺ > Pb²⁺ > Cd²⁺) as they coexisted. The influence of initial pH of wastewater for the removal efficiency of metal ions was also investigated and a pH > 7 was preferred.     

Removal of Hg(II) from acid aqueous solutions by poly(N‐vinylimidazole) hydrogel

Caption of Hg(II) from acid aqueous solution by immersed poly(N‐vinylimidazole) hydrogel particles was studied as a function of pH, counterion, and cation concentration. Fitting parameters to several sorption isotherms have been determined. Their values depend mostly on pH and less, on temperature and counterion, and suggest a large affinity of imidazole groups in the gel and mercury cations. Practically total removal (94.4%) of Hg(II) is achieved at pH = 2, with 10 g of dry gel per liter of solution, when cation concentration was as large as 15,000 ppm (0.075 M). Polymer protonation decreases about fourfold the cation affinity, supporting competitive protonation‐complexation mechanisms. By its side, metal uptake decreases polymer protonation. Thermal stability of loaded gels decreases with respect to metal free hydrogels. Scanning electron micrographs reveal no changes in the gel morphology upon cation binding, but T_g increases significantly with the Hg(II) content of loaded gels and swelling decreases moderately, indicating the role of the cation as ionic crosslinker. Practically total elution of Hg(II) is achieved with 1 M HNO₃ in consecutive loading‐elution cycles. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1467–1475, 2001     

Hydrogel beads based on carboxymethyl cellulose for removal heavy metal ions

Environment‐friendly carboxymethyl cellulose (CMC) hydrogel beads were successfully prepared using epichlorohydrin (ECH) as a crosslinking agent in the suspension of fluid wax. There was an ether linkage formed between ECH and CMC, which was identified from bands in FTIR spectra of the prepared hydrogel. The prepared hydrogel beads with diameters about 4 mm were apparently spherical and fully transparent. The X‐ray diffraction (XRD) spectra indicated that the adsorption of metal ion onto the oxygen atom of carboxyl group led to change in crystallinity patterns of hydrogels. The scanning electron microscope (SEM) images clearly showed that the hydrogels had an internal porous structure. The adsorption capacity increased as initial concentrations of metal ions and the pH value of metal ion solution increased. Freundlich and Langmuir isotherm models were employed to analyze the data from batch adsorption experiments. There are vey good correlation coefficients of linearized equations for Langmuir model, which indicated that the sorption isotherm of the hydrogel beads for metal ions can be fitted to the Langmuir model. The maximum adsorption amount of hydrogel beads for metal ions is 6.49, 4.06, and 5.15 mmol/g for Cu(II), Ni(II), and Pb(II), respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011